JPH10182938A - Curable resin composition and resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cold-curing resin composition capable of controlling the pot life without varying the initial viscosity and the properties of cured product and having extremely high adhesivity to wet surface. SOLUTION: This curable resin composition contains an epoxy resin, a polyfunctional (meth)acrylate compound having hydroxyl group, a polyfunctional (meth)acrylate compound free from hydroxyl group and a polyfunctional amine compound having active hydrogen or this resin composition contains an epoxy resin, a polyfunctional (meth)acrylate compound having hydroxyl group and a polyfunctional, (meth)acrylate compound free from hydroxyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hardening surface for civil engineering and construction materials such as concrete and mortar, which is hardened at room temperature.
A curable resin composition that can control the curing time without greatly changing the initial viscosity and physical properties after curing, and is useful as an adhesive, repair material, water-blocking material for injection, floor coating, joint filler, and paint that exhibits excellent adhesion. And a resin composition as a main agent thereof.

[0002]

2. Description of the Related Art Conventionally, epoxy resin has been used for concrete,
Because of its excellent adhesion to mortar, etc., it can be used for adhesives for civil engineering construction, water-blocking materials for injection, repair materials, painted floor materials, jointing agents,
It is frequently used as a paint. However, in the field of civil engineering and construction, the adherends and objects to be applied are basically hydraulic, and are close to water sources such as rainfall, groundwater, rivers and coasts. The surface and inside are often wet. As a result, while the reaction of the epoxy resin is accelerated by water, the presence of water at the interface between the epoxy resin and the adherend hinders the wetting of the epoxy resin and the adherend surface and significantly reduces the adhesive force. I do.

Japanese Patent Application Laid-Open No. 57-12024 discloses a method for improving the adhesion to a water-wet surface by mixing cement with an epoxy resin mixture comprising a liquid epoxy resin and an amine curing agent. There is a problem that it takes a long time of several tens minutes or more to cure at room temperature. Japanese Patent Application Laid-Open No. 62-252488 discloses an acrylic resin material which is capable of radical polymerization at a low temperature by blending a redox initiator and cement in an aqueous solution of a polyvalent metal salt of (meth) acrylic acid. Although the composition is disclosed, the pot life is short because the curing speed is very fast, and when used in large quantities, there are restrictions such as the necessity of a special device such as applying or pouring simultaneously with compounding. It is difficult to control the curing time of any of the above compositions, and it is necessary to control the curing speed by changing the resin composition in order to adjust the required pot life according to the application or application conditions. Occurs.

[0004]

SUMMARY OF THE INVENTION The present invention provides a room-temperature-curable resin composition which can control the pot life without changing the initial viscosity and physical properties after curing, and has a very high adhesive strength to a wet surface. Aim.

[0005]

Means for Solving the Problems The present inventors have developed a polyfunctional (meth) acrylate compound in a curable resin composition containing an epoxy resin, a polyfunctional (meth) acrylate compound and a polyfunctional amine compound having active hydrogen. By using a combination of a polyfunctional (meth) acrylate compound with a hydroxyl group and a polyfunctional (meth) acrylate compound without a hydroxyl group, the curing speed can be easily controlled without changing the initial viscosity and the physical properties after curing. , Found that it can be used under conditions with different pot life.
The present invention has been reached.

The curing rate is controlled by the effect that the (meth) acryloyl group of the polyfunctional (meth) acrylate compound is activated by active hydrogen of the hydroxyl group, and the nucleophilic reaction by the polyfunctional amine compound, ie, the Michael reaction is promoted. Specifically, it is carried out by adjusting the blending ratio of a polyfunctional (meth) acrylate compound having a hydroxyl group and a polyfunctional (meth) acrylate compound having no hydroxyl group. In the present invention, the (meth) acryloyl group represents a methacryloyl group or an acryloyl group, and the (meth) acrylate compound represents a methacrylate compound or an acrylate compound.

That is, the present invention provides a) an epoxy resin,
The present invention relates to a curable resin composition containing b) a polyfunctional (meth) acrylate compound having a hydroxyl group, c) a polyfunctional (meth) acrylate compound having no hydroxyl group, and d) a polyfunctional amine compound having active hydrogen. The present invention also relates to the curable resin composition containing a silane compound having an epoxy group. The present invention also relates to the curable resin composition containing a silane compound having an amino group.

Further, the present invention provides Xa ≦ Y where Xa is the number of (meth) acryloyl groups, Xe is the number of epoxy groups, and Y is the number of active hydrogens of amino groups contained in the resin composition.
≦ (Xa + Xe) Further, the present invention relates to a resin composition containing a) an epoxy resin, b) a polyfunctional (meth) acrylate compound having a hydroxyl group, and c) a polyfunctional (meth) acrylate compound having no hydroxyl group.

In the curable resin composition of the present invention, the Michael reaction is further promoted under water and alkaline conditions. It has an excellent feature that the reaction is accelerated by mixing with the wet concrete surface or inside the gap or by mixing with the cement slurry, and it hardens in a short time.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The curable resin composition of the present invention comprises:
a) an epoxy resin, b) a base agent containing a polyfunctional (meth) acrylate compound having a hydroxyl group and c) a polyfunctional (meth) acrylate compound having no hydroxyl group, and d) a polyfunctional amine compound having active hydrogen. It is used as a two-pack type curable resin composition which is mixed with a curing agent when used. The curable resin composition of the present invention may be in a liquid state in a state where the above main agent and the curing agent are mixed.
To obtain excellent cured properties by mixing quickly and uniformly, both the base resin and the curing agent must be in a liquid state and the viscosity in the mixed state must be low.
It is desirable to be 100-1000 cps (25 ° C). In addition,
The liquid referred to here includes not only a liquid in which two or more kinds of compounds are completely compatible with each other and a liquid, but also a heterogeneous system in which a powdery compound is dispersed in a liquid compound.

As the compound contained in the curable resin composition of the present invention, any compound can be used as long as it is liquid at the time of mixing. Flash point 70 ~ 300 ℃
It is desirable to use those which have low odor of (dangerous goods, Class 4 petroleum, fourth petroleum).

A) As the epoxy resin, a liquid or solid epoxy resin at normal temperature can be used. Epoxy coat 801, Epicoat 807, Epicoat 80 manufactured by Yuka Shell Epoxy Co., Ltd.
8, Epicort 815, Epicort 816, Epicort 819, Epicort 876, Epicort 828, Epicort 834, Araldite GY-257, Araldite GY-252 manufactured by Ciba-Gaiky Co., Ltd.
Araldite GY-250, Araldite GY-260, Araldide GY-280, DER324 manufactured by Dow Chemical Japan Co., Ltd.
ER331, DER331C, DER332, DER334, DE
R.335, DER336, DER337, DER353J, DER7
32, DER736 etc., liquid bisphenol type epoxy resin, Denasel EX-411, Denacol EX-421, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-201, Denacol EX of Nagase Kasei Kogyo Co., Ltd. -twenty one
1, Denacol EX-810, Denacol EX-811, Denacol E
X-850, Denacol EX-851, Denacall EX-821, Denacall EX-830, Denacall EX-832, Denacall EX-911, Denacall EX-941, Denacall EX-920, Denacall EX-92
1, polyglycidyl ether type epoxy compounds such as Denacol EX-931, Denacol EX-2000 and Denacol EX-992, and mixtures thereof, but are not necessarily limited thereto.

As the epoxy resin which is solid at room temperature, there are Epicoat 864 and Epicoat 10 manufactured by Yuka Shell Epoxy Co., Ltd.
01, Epikote 1004, Epikote 1007, Epikote 100
9, Epicoat 1310, Araldite GY-6040, Araldite GY-6060, Araldite GY-607 manufactured by Ciba-Gaiky Corporation
1, araldide GY-6075, araldide GY-6084, araldite GY-6097, araldide GY-6099, a liquid bisphenol type epoxy resin such as DER661, DER664, DER667 manufactured by Dow Chemical Japan, or a mixture thereof. However, the present invention is not necessarily limited to these.

B) As the polyfunctional (meth) acrylate compound having a hydroxyl group, a polyhydric alcohol having a valence of 3 or more, preferably 6 or less, may be obtained by adding acrylic acid or methacrylic acid so that at least one hydroxyl group remains. A compound esterified with an acid and an epoxy group
An epoxy (meth) acrylate obtained by adding (meth) acrylic acid to an epoxy resin having at least one epoxy resin is used. Specific examples of compounds obtained by esterifying a polyhydric alcohol with (meth) acrylic acid include pentaerythritol di (meth) acrylate and pentaerythritol tri (meth)
Examples include acrylate, 3-acryloyloxyglycerin mono (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate, but are not necessarily limited thereto. The curable resin composition of the present invention utilizes the Michael addition reaction between the (meth) acryloyl group and the active hydrogen of the polyfunctional amine compound as the first-stage crosslinking reaction, so that highly reactive acrylate compounds are preferably used. Is done.

C) The polyfunctional (meth) acrylate compound having no hydroxyl group is a compound obtained by esterifying all hydroxyl groups of a polyhydric alcohol, preferably a dihydric to hexahydric alcohol with acrylic acid or methacrylic acid. It is. Specifically, 1,6-hexanediol di (meth)
Acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Ethylene oxide modified bisphenol A diacrylate, propylene oxide modified bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylol Examples include, but are not necessarily limited to, propane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyvalent metal salts of (meth) acrylic acid, and mixtures thereof. The curable resin composition of the present invention utilizes the Michael addition reaction between the (meth) acryloyl group and the active hydrogen of the polyfunctional amine compound as the first-stage crosslinking reaction, so that highly reactive acrylate compounds are preferably used. Is done.

The viscosity of the resin composition (base agent) containing the above a), b) and c) is desirably 100 to 1000 cps (at 25 ° C.). When the viscosity is lower than 100 cps, it is difficult to adhere to the base material, and when the viscosity is higher than 1000 cps, the workability of d) mixing with a curing agent containing a polyfunctional amine compound having active hydrogen, and applying and pouring to the base material is deteriorated. . The viscosity can be adjusted by selecting the material. a) When a solid epoxy resin is used at room temperature, an organic solvent is preferably used. Examples of the organic solvent include isopropyl alcohol, methyl ethyl ketone, xylene, and ethyl acetate.

The curable resin composition of the present invention preferably contains a silane compound having an epoxy group in order to improve the adhesive strength. The silane compound having an epoxy group is contained in a resin composition (base material) containing the above a), b) and c). The silane compound having an epoxy group is a silane coupling agent having an epoxy group and an alkoxysilyl group, and specifically, β- (3,
4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropyltriemethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and the like, but are not necessarily limited thereto.

The silane compound having an epoxy group is a)
The ratio of the number of epoxy groups of the silane compound having an epoxy group to the total number of epoxy groups of the epoxy resin and b), c) the (meth) acryloyl groups of the polyfunctional (meth) acrylate compound becomes 0.01 to 0.3. It is desirable to mix them. When the ratio of the number of epoxy groups in the silane compound having an epoxy group is less than 0.01, the effect of improving the adhesive strength is low. On the other hand, if it exceeds 0.3, condensation of the alkoxysilyl groups promoted by the alkali and moisture of the substrate occurs preferentially over the Michael addition reaction, the curing reaction of the epoxy resin, and the reaction of the alkoxysilyl group with the substrate. As a result, the wettability deteriorates and the siloxane bond becomes dense, the film becomes brittle and the adhesive strength decreases.

D) The polyfunctional amine compound having active hydrogen is a polyfunctional amine compound having two or more primary or secondary amino groups, and a liquid compound at room temperature can be suitably used. Considering the workability when mixing, applying or pouring with the main agent, it is desirable to use one with a viscosity of 5 to 1000 cps (25 ° C). Considering the working environment and safety, it is desirable to use those with a flash point of 70 to 300 ° C (hazardous substances, Class 4 and 3 petroleums, and petroleums 4) with low odor. Specifically, isophoronediamine (IPDA), bis (4-amino-3-methylcyclohexyl) methane, 4,4′-bis (p-aminocyclohexyl) methane, and Jeffamine D-230 manufactured by Jefferson Chemical Co., Ltd. , Jeffamine D-4
Examples include polyoxyalkyleneamines such as 00, Jeffamine D-2000, and Jeffamine T-403, but are not necessarily limited thereto.

The curable resin composition of the present invention preferably contains a silane compound having an amino group in order to improve the adhesive strength. The silane compound having an amino group is contained in a curing agent containing the above d). The silane compound having an amino group is a silane coupling agent having an amino group and an alkoxysilyl group. Specifically, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (amino Ethyl) -γ-aminopropyltrimethoxysilane, N-β
-(Aminoethyl) -γ-aminopropyltriethoxysilane, and the like, but are not necessarily limited thereto.

The silane compound having an amino group is d) so that the ratio of the number of active hydrogens of the silane compound having an amino group to the number of active hydrogens of the polyfunctional amine compound having an active hydrogen is 0.01 to 0.3. It is desirable to mix. When the ratio of the number of active hydrogen atoms of the silane compound having an amino group is less than 0.01, the effect of improving the adhesive strength is low. On the other hand, if it exceeds 0.3, condensation of the alkoxysilyl groups promoted by the alkali and moisture of the substrate occurs preferentially over the Michael addition reaction, the curing reaction of the epoxy resin, and the reaction of the alkoxysilyl group with the substrate. As a result, the wettability deteriorates and the siloxane bond becomes dense, the film becomes brittle and the adhesive strength decreases.

Each of the components constituting the curable resin composition of the present invention has a number of (meth) acryloyl groups Xa, a number of epoxy groups Xe, and a number of active hydrogens of amino groups contained in the resin composition. Assuming that Y, it is desirable to mix them so that Xa ≦ Y ≦ (Xa + Xe). If Y <Xa (meta)
Acryloyl groups remain and curing is incomplete.
In the case of (Xa + Xe), unreacted amine remains to deteriorate water resistance. To balance the curing speed and the durability of the cured product, (Xa + Xe) = Y, and further, Xa = Xe = Y × Ｙ.
Is desirable. By blending such that Xa = Xe = Y × 1/2, a resin composition having a good balance between the pot life and the adhesion and durability on a wet surface can be obtained.

The curable resin composition of the present invention may contain various additives for various purposes. For example, fillers, diluents or resin components are added to improve cured physical properties, viscosity control or cost reduction, and antibacterial agents, fungicides or preservatives are added to give added value, or coloring is used. A pigment may be added, and a polymerization inhibitor may be added to suppress radical polymerization of the (meth) acryloyl group. In addition, by adding an additive component which reacts with the main component essential component but does not react with the hardener essential component to the curing agent, and an additional component which reacts with the hardener essential component but does not react with the main component essential component to the main component, respectively. Storage stability and reactivity after mixing and cured physical properties can be improved.

In order to control the curing time, several kinds of polyfunctional amine compounds having different curing rates can be blended in the curing agent. However, it is not suitable when the same performance as when the curing time is not controlled is required, because it requires drastic changes in the formulation and affects the physical properties after curing such as viscoelasticity.

[0025]

The present invention will be described in more detail with reference to the following examples. Examples include those not containing a silane compound [Example 1], those containing a silane compound having an amino group [Examples 2 and 3], and those containing a silane compound having an epoxy group [Example 4]. about,
The following measurements were performed while changing the mixing ratio of b) and c).
In addition, as comparative examples, those containing only a polyfunctional (meth) acrylate compound c) and containing a silane compound having an amino group [Comparative Example 1] and those containing only b) as a polyfunctional (meth) acrylate compound and containing an amino group The following measurement was carried out in the same manner as in the example, except that the compounding ratio of the polyfunctional amine compound was changed for the sample containing the silane compound having the formula [Comparative Example 2]. The abbreviations described in the prescription indicate the following.

A) Epoxy resin EP828 = liquid bisphenol A type epoxy resin (“Epicoat 828” manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 185 g / eqiv.) B) Polyfunctional (meth) acrylate compound having a hydroxyl group M305 = Pentaerythritol triacrylate (“Aronix M-305” manufactured by Toa Gosei Chemical Industry Co., Ltd., acryloyl equivalent 99.3 g / eqiv.) C) Polyfunctional (meth) acrylate compound without hydroxyl group M309 = Trimethylolpropanetri Acrylate ("Aronix M-309" manufactured by Toa Gosei Chemical Industry Co., Ltd., acryloyl equivalent 98.7 g / eqiv.) SR355 = Ditrimethylolpropane tetraacrylate ("Sartomer 355" manufactured by Nippon Kayaku Co., Ltd., acroyl equivalent 116.5 g / eqiv.)

A silane compound having an epoxy group KBM403 = γ-glycidoxypropyltrimethoxysilane (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd., epoxy equivalent: 23)
6.3 g / eqiv.) D) Polyfunctional amine compound having active hydrogen IPDA = isophoronediamine (Hüls Japan K.K.)
"Vestamine IPD", active hydrogen equivalent 42.5 g / eqiv.) D400 = polyoxypropylene diamine ("Jeffamine D-400", manufactured by San Techno Chemical Co., Ltd., active hydrogen equivalent 100 g / eqiv.) Amino group-containing silane Compound KBE903 = γ-aminopropyltriethoxysilane (“KBE-903” manufactured by Shin-Etsu Chemical Co., Ltd., active hydrogen equivalent: 110.7 g / e)
qiv.)

[Test of Adhesive Strength to Wet Mortar] A commercially available concrete plate (40 cm × 40 cm × 5 cm) was immersed in water for one day, and the surface of the concrete was gently wiped off with a water surface 5 mm below the surface. The adhesive surface was divided into a total of 16 sections, 4 in length and 4 in width, and an adhesive strength test was performed using the outer 12 places where the back water pressure was strictest. The compounded curable resin composition was applied to a metal adhesive plate having a length of 2 cm and a width of 2 cm and adhered to concrete. After leaving it at room temperature for one week, the adhesive strength and peeling state were measured using a Kenken-type adhesive peeling tester.

[Measurement of Curing Time with and without Cement] 10 g of the compounded curable resin composition was allowed to stand at room temperature to measure the time until gelation. In addition, cement 3
g and 7 g of water were mixed with 10 g of the curable resin composition, and the curing time was measured. [Measurement of dynamic viscoelasticity] The compounded curable resin composition has a thickness
The mixture was poured into a circular pallet of about mm to form a pellet. After giving a curing time of one week at room temperature, it was taken out and cut into a size of 5 mm in width and 30 mm in length. The dynamic viscoelasticity was measured using this sample. Measurement temperature is -100
C. to 100.degree.

Example 1 According to the formulation shown in Table 1-1,
By changing the mixing ratio of b) pentaerythritol triacrylate and c) ditrimethylolpropane tetraacrylate, four types of curable resin compositions were prepared. In addition,
The main agent and the hardener were stored in separate containers and sealed at 25 ° C for a long time without viscosity increase or gelation. Using the obtained curable resin composition, an adhesion strength test to a wet concrete plate, a curing time measurement, and a dynamic viscoelasticity measurement of the cured product were performed.
The results are shown in Table 1-2. The measurement results of the viscosity increase and the setting time using the cement slurry show that the larger the amount of pentaerythritol triacrylate is added, the shorter the setting time. However, the viscoelasticity and adhesive strength of the cured product did not change significantly.

[0031]

[Table 1]

Example 2 According to the formulation shown in Table 2-1
The compounding ratio of b) pentaerythritol triacrylate and c) trimethylolpropane triacrylate is changed to include a silane compound having an amino group as a curing agent.
Various curable resin compositions were prepared. The main agent and the curing agent could be stored at 25 ° C. for a long time without increasing the viscosity or gelling at 25 ° C. by sealing them in separate containers. The same evaluation as in Example 1 was performed using the obtained curable resin composition. The results are shown in Table 2-2. The measurement results of the viscosity increase and the setting time using the cement slurry show that the larger the amount of pentaerythritol triacrylate is added, the shorter the setting time.
However, the viscoelasticity and adhesive strength of the cured product did not change significantly. Further, since the composition contains a silane compound having an amino group, the composition has high adhesive strength.

[0033]

[Table 2]

Example 3 According to the formulation shown in Table 3-1
By changing the mixing ratio of b) pentaerythritol triacrylate and c) ditrimethylolpropane tetraacrylate, four types of curable resin compositions containing a silane compound having an amino group as a curing agent were prepared. The main agent and the curing agent could be stored at 25 ° C. for a long time without increasing the viscosity or gelling at 25 ° C. by sealing them in separate containers. The same evaluation as in Example 1 was performed using the obtained curable resin composition. The results are shown in Table 3-2. The measurement results of the viscosity increase and the setting time using the cement slurry show that the larger the amount of pentaerythritol triacrylate is added, the shorter the setting time.
However, the viscoelasticity and adhesive strength of the cured product did not change significantly. Further, since the composition contains a silane compound having an amino group, the composition has high adhesive strength.

[0035]

[Table 3]

Example 4 According to the formulation shown in Table 4-1
By changing the mixing ratio of b) pentaerythritol triacrylate and c) ditrimethylolpropane tetraacrylate, four types of curable resin compositions containing a silane compound having an epoxy group as a main component were prepared. The main agent and the curing agent could be stored at 25 ° C. for a long time without increasing the viscosity or gelling at 25 ° C. by sealing them in separate containers. The same evaluation as in Example 1 was performed using the obtained curable resin composition. The results are shown in Table 4-2. The measurement results of the viscosity increase and the setting time using the cement slurry show that the larger the amount of pentaerythritol triacrylate is added, the shorter the setting time.
However, the viscoelasticity and adhesive strength of the cured product did not change significantly. Further, since the composition contains a silane compound having an epoxy group, the composition has high adhesive strength.

[0037]

[Table 4]

Comparative Example 1 According to the formulation shown in Table 5-1
C) Only ditrimethylolpropane tetraacrylate is used as the polyfunctional (meth) acrylate compound, and the mixing ratio of isophoronediamine and Jeffamine D400 in the curing agent is changed. A curable resin composition was prepared. In addition,
The main agent and the hardener were stored in separate containers and sealed at 25 ° C for a long time without viscosity increase or gelation. The same evaluation as in Example 1 was performed using the obtained curable resin composition. The results are shown in Table 5-2. It can be seen that the greater the amount of isophoronediamine, the faster it cures and the higher the Tg of the cured product.
In addition, since only ditrimethylolpropanetetraacrylate is used as the polyfunctional (meth) acrylate compound, curing is moderate, but there is almost no difference in adhesive strength, and the composition contains a silane compound having an amino group in the composition. Therefore, it shows high adhesive strength.

[0039]

[Table 5]

[Comparative Example 2] According to the formulation shown in Table 6-1
Using only b) pentaerythritol triacrylate as a polyfunctional (meth) acrylate compound, changing the blending ratio of isophoronediamine and Jeffamine D400 in the curing agent, and curing four types including a silane compound having an amino group in the curing agent. A resin composition was prepared. The main agent and the curing agent could be stored at 25 ° C. for a long time without increasing the viscosity or gelling at 25 ° C. by sealing them in separate containers. The same evaluation as in Example 1 was performed using the obtained curable resin composition. Table 6-2 shows the results.
Shown in It can be seen that the greater the amount of isophoronediamine, the faster it cures and the higher the Tg of the cured product. Also,
Since only pentaerythritol triacrylate is used as the polyfunctional (meth) acrylate compound, curing is very fast, but there is almost no difference in adhesive strength, and the composition contains a silane compound having an amino group. It shows the adhesive strength.

[0041]

[Table 6]

[0042]

The curable resin composition of the present invention does not cure independently of the main agent and the curing agent alone, but changes the compounding ratio of the polyfunctional (meth) acrylate compound b) and c) in the main agent to change the curing time. Is controlled, so that the pot life can be adjusted. When the curable resin composition of the present invention comes into contact with a wet surface such as concrete or mortar, or mixes with a cement slurry,
Micha with acryloyl group and amino group having active hydrogen
The el addition reaction is accelerated, and the heat of the reaction accelerates the addition reaction between the epoxy group and the amino group having active hydrogen and the ring-opening polymerization of the epoxy group to cure, resulting in excellent adhesion and water resistance even on a wet surface. It has the characteristic of exhibiting properties. Further, the curable resin composition of the present invention containing a silane compound having an amino group or a silane compound having an epoxy group can be obtained by reacting the epoxy group of the silane compound having an epoxy group with the amino group, Since the amino group reacts with the (meth) acryloyl group or the epoxy group, an alkoxysilyl group is introduced into the cured product,
Adhesion with inorganic substances is improved. The curable resin composition of the present invention can be used especially when the same skeleton is used as the polyfunctional (meth) acrylate compounds b) and c).
Since the curing time can be controlled without changing the adhesiveness and dynamic viscoelasticity of the obtained cured product, it is extremely useful in the fields of construction and civil engineering, and has high versatility.

Claims (5)

[Claims] 1. A) an epoxy resin, b) a polyfunctional (meth) acrylate compound having a hydroxyl group, c) a polyfunctional (meth) acrylate compound having no hydroxyl group, and d) a polyfunctional amine compound having active hydrogen A curable resin composition comprising: 2. The curable resin composition according to claim 1, comprising a silane compound having an epoxy group. 3. The curable resin composition according to claim 1, comprising a silane compound having an amino group. 4. Assuming that the number of (meth) acryloyl groups contained in the resin composition is Xa, the number of epoxy groups is Xe, and the number of active hydrogens of amino groups is Y, Xa ≦ Y ≦ (Xa + Xe).
The curable resin composition according to any one of claims 1 to 3, wherein 5. A resin composition comprising: a) an epoxy resin; b) a polyfunctional (meth) acrylate compound having a hydroxyl group; and c) a polyfunctional (meth) acrylate compound having no hydroxyl group.